Intensification of Ethyl Esters Synthesis Using a Packed-Bed Tubular Reactor at Supercritical Conditions
In the present study, the non-catalytic transesterification of soybean oil in continuous mode using supercritical ethanol were investigated. Experiments were performed in a packed-bed tubular reactor (PBTR) and variable studied were reaction temperature (523 K to 598 K), pressure (10 MPa to 20 MPa), oil to ethanol molar ratio (1:10 to 1:40) and water concentration (0 wt% to 10 wt% in ethanol). Results showed that ethyl esters yields obtained in the PBTR were higher (> 20 wt%) than those verified in a tubular reactor (TR), due to improved mass transfer conditions attained in the PBTR. Results demonstrated that temperature, pressure, oil to ethanol molar ratio and water concentration had a positive effect on fatty acid ethyl esters (FAEE) production in the experimental range investigated, with appreciable reaction yields (90 wt%) achieved at 598 K, 20 MPa, oil to ethanol molar ratio of 1:40 and 10 wt% of water concentration.
Digital Object Identifier (DOI): doi.org/10.5281/zenodo.1127569Procedia APA BibTeX Chicago EndNote Harvard JSON MLA RIS XML ISO 690 PDF Downloads 696
 T. Pinnarat, P. Savage, “Assessment of noncatalytic biodiesel synthesis using supercritical reaction conditions,” Ind. Eng. Chem. Res, vol. 47, pp. 6801-6808, 2008.
 D. Wen, H. Jiang, K. Zhang, K, “Supercritical fluids technology for clean biofuel production,” Prog. Nat. Sci, vol. 19, pp. 273-284, 2009.
 H. Imahara, E. Minami, S. Hari, S. Saka, “Thermal stability of biodiesel in supercritical methanol,” Fuel, vol. 87, pp. 1-6, 2007.
 I. Vieitez, C. Silva, I. Alkimim, F. Castilhos, J.V. Oliveira, M.A. Grompone, I. Jachmanián, “Stability of ethyl esters from soybean oil exposed to high temperatures in supercritical ethanol,”J. Supercrit. Fluid, vol. 56, pp. 265–270, 2011.
 P. Olivares-Carrillo, J. Quesada-Medina, “Synthesis of biodiesel from soybean oil using supercritical ethanol in a one-step catalyst-free process in batch reactor”J. Supercrit. Fluid., vol. 58, pp. 378-384, 2011.
 H. Shin, S. Lim, S.Bae, S.C. Oh, “Thermal decomposition and stability of fatty acid methyl esters in supercritical methanol,”J. Anal. Appl. Pyrol., vol. 92, pp. 332–338, 2011.
 G. Anitescu, A. Deshpande, L.L.Tavlarides, “Integrated technology for supercritical biodiesel production and power cogeneration,”Energy & Fuel, vol. 22, pp. 1391-1399, 2008.
 N. Aimaretti, D.I. Manuale, V.M.Mazzieri, C.R. Vera, C.Yori, “Batch Study of Glycerol Decomposition in One-Stage Supercritical Production of Biodiesel,”Energy & Fuel,vol. 23, pp. 1076-1080, 2009.
 N.S. Kasim, T.H. Tsai, S.Gunawan, Y.H.Ju, “Biodiesel production from rice bran oil and supercritical methanol,”Bioresour. Technol.,vol. 100, pp. 2007–2011, 2009.
 V.F. Marulanda, G.Anitescu, L.L.Tavlarides, “Investigations on supercritical transesterification of chicken fat for biodiesel production from lowcost lipid feedstocks,”J. Supercrit. Fluid.,vol. 54, pp. 53–60, 2010.
 D. Kusdiana, S. Saka, “Biodiesel fuel from rapeseed oil as prepared in supercritical methanol,”Fuel,vol. 80, pp. 225-231, 2001.
 E. Minami, S. Saka, “Kinetics of hydrolysis and methyl esterification for biodiesel production in two-step supercritical methanol process,”Fuel,vol. 85, pp. 2479-2483, 2006.
 H. He, W. Tao, S. Zhu, “Continuous production of biodiesel from vegetable oil using supercritical methanol process,”Fuel,vol. 86, pp. 442-447, 2007.
 C. Silva, T.A. Weschenfelder, S. Rovani, F.C. Corazza, M.L. Corazza, C. Dariva, J.V. Oliveira, “Continuous production of fatty acid ethyl esters from soybean oil in compressed ethanol”Ind. Eng. Chem. Res.,vol. 46, pp. 5304-5309, 2007.
 I. Vieitez, M.J. Pardo, C. Silva, C.Bertoldi, F. Castilhos, J.V.Oliveira, M.A. Grompone, I. Jachmanián, “Continuous synthesis of castor oil ethyl esters under supercritical ethanol,”J. Supercrit. Fluid., vol. 56, pp. 271–276, 2011.
 W. Cao, H. Han, J. Zhang, “Preparation of biodiesel from soybean oil using supercritical methanol and co-solvent,”Fuel,vol. 84, pp. 347-351, 2005.
 P.Hegel, G.Mabe, S.Pereda, E.A.Brignole, “Phase transitions in a biodiesel reactor using supercritical methanol,”Ind. Eng. Chem. Res.,vol. 46, pp. 6360-6365, 2007.
 J.Z. Yin, M. Xiao, J.B. Song, “Biodiesel from soybean oil in supercritical methanol with co-solvent,”Energy Convers. Manag., vol. 49, pp. 908-912, 2007.
 C. Bertoldi, C. Silva, J.P. Bernardon, M.L. Corazza, L. Cardozo Filho, J.V. Oliveira, F.C. Corazza, “Continuous Production of Biodiesel from Soybean Oil in Supercritical Ethanol and Carbon Dioxide as Co-solvent,” Energy & Fuels, vol. 23, pp. 5165-5172, 2009.
 C.M. Trentin, A.P. Lima, I.P. Alkimim, C. Silva, F. Castilhos, M.A. Mazutti, J.V. Oliveira, “Continuous catalyst-free production of fatty acid ethyl esters from soybean oil in microtube reactor using supercritical carbon dioxide as co-solvent,”J. Supercrit. Fluid.,vol. 56, pp. 283-291, 2011.
 S.A. Ippolito, J.C.Yori, M.E.Iturria, C.L.Pieck, C.R. Vera,“Analysis of a two-step, non-catalytic, supercritical biodiesel production process with heat recovery,”Energy & Fuels,vol. 21, pp. 339-346, 2007.
 C. Silva, A.P Lima, F. Castilhos, L. Cardozo Filho, J.V. Oliveira, “Non-catalytic production of fatty acid ethyl esters from soybean oil with supercritical ethanol in a two-step process using a microtube reactor,”Biomass Bioenerg, vol. 35, pp. 526-532, 2011.
 D. Kusdiana, S. Saka, “Two-step preparation for catalyst-free biodiesel fuel production,”Appl. Biochem. Biotechonol.,vol. 113, pp. 781-791, 2004.
 C. Chen, W. Chen, C.J. Chang, S. Lai, C. Tu, “Biodiesel production from supercritical carbon dioxide extracted Jatropha oil using subcritical hydrolysis and supercritical methylation,”J. Supercrit. Fluid,vol. 52, pp. 228–234, 2010.
 C. Silva, F. Castilhos, J.V. Oliveira, L. Cardozo Filho, “Continuous production of soybean biodiesel with compressed ethanol in a microtube reactor,”Fuel Process.Technol., vol. 91, pp. 1274-1281, 2010.
 C.M. Trentin, A.P. Lima, I.P. Alkimim, C. Silva, F. Castilhos, M.A. Mazutti, J. V. Oliveira, “Continuous production of soybean biodiesel with compressed ethanol in a microtube reactor using carbon dioxide as co-solvent,”Fuel Process.Technol.,vol. 92, pp. 952-958, 2011.
 E. Achenbach,“Heat and Flow Characteristics of Packed Beds,”Exp. Therm. Fluid. Sci.,vol. 10, pp. 17-27, 1994.
 Y. Su, “The Intensification of Rapid Reactions for Multiphase Systems in a Microchannel Reactor by Packing Microparticles,”AIChE J.,vol. 57, pp. 1409–1418, 2011.
 F. Ataya, M.A. Dube, M. Ternan, “Transesterification of Canola Oil to Fatty Acid Methyl Ester (FAME) in a Continuous Flow Liquid-Liquid Packed Bed Reactor,”Energy & Fuels,vol. 22, pp. 3551–3556, 2008.
 Standard UNE-EN 14103,“Determination of ester and linolenic acid methyl ester contents, issued by Asociación Española de Normalización y Certificación,” Madrid, 2003.
 K.T. Tan, K.T., Lee, A.R. Mohamed, “Production of FAME by palm oil transesterification via supercritical methanol technology,”Biomass Bioenerg.,vol. 33, pp. 1096-1099, 2009.
 M.M. Gui, K.T. Lee, S. Bhatia, “Supercritical ethanol technology for the production of biodiesel: process optimization studies,”J. Supercrit. Fluid., vol. 49, pp. 286-292, 2009.
 R. Sawangkeaw, S. Teeravitud, K.Bunyakiat, S. Ngamprasertsith, “Biofuel production from palm oil with supercritical alcohols: Effects of the alcohol to oil molar ratios on the biofuel chemical composition and properties,”Bioresource Technol.,vol. 102, pp. 10704–10710, 2011.
 C. Choi, J. Kim, C.Jeong, H. Kim, K. Yoo, “Transesterification kinetics of palm olein oil using supercritical methanol,”J. Supercrit. Fluid., vol. 58, pp. 365-370, 2011.
 I. Vieitez, C. Silva, I. Alkimim, G.R. Borges, F.C. Corazza, J.V. Oliveira, M.A. Grompone, I. Jachmanián, “Effect of temperature on the continuous synthesis of soybean esters under supercritical ethanol,”Energy & Fuels,vol. 23, pp. 558-563, 2009.
 I. Vieitez, C. Silva, G.R. Borges, F.C.Corazza, J.V. Oliveira, M.A. Grompone, I.Jachmanián, “Continuous production of soybean biodiesel in supercritical ethanol-water mixtures,”Energy & Fuels, vol. 22, pp. 2805-2809, 2008.
 A. Demirbas, “Biodiesel production via non-catalytic SCF method and Biodiesel fuel characteristics,”Energy Convers. Manag., vol. 47, pp. 2271-2282, 2006.
 I. Vieitez, C. Silva, I.Alkimim, G.R. Borges, F.C.Corazza, J.V. Oliveira, M.A.Grompone, I.Jachmanián, “Continuous catalyst-free methanolysis and ethanolysis of soybean oil under super critical alcohol/water mixtures,”Renew. Energ., vol. 35, pp. 1976–1981, 2010.
 A. Velez, G. Soto, P. Hegel, G. Mabe, S. Pereda, “Continuous production of fattya acid ethyl ésteresfrom sunflower oil using supercritical ethanol,” Fuel, vol. 97, pp. 703-709, 2012.